US11276877B2ActiveUtilityPatentIndex 59

Stabilized birnessite cathode for high power and high energy density applications

Assignee: UNIV CITY NEW YORK RES FOUNDPriority: Mar 15, 2017Filed: May 4, 2018Granted: Mar 15, 2022

Est. expiryMar 15, 2037(~10.7 yrs left)· nominal 20-yr term from priority

Inventors:YADAV GAUTAM G NYCE MICHAEL HUANG JINCHAO COUZIS ALEXANDER BANERJEE SANJOY

H01M 10/0525C01P 2002/54H01M 4/0471H01M 4/525H01M 10/054H01M 4/505H01M 10/052H01M 2004/021H01M 4/625H01M 4/622H01M 4/623H01M 4/131H01M 10/128H01M 4/1391Y02E60/10C01P 2002/20C01G 45/02H01M 4/661

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Claims

Abstract

A battery comprises a housing, an electrolyte disposed in the housing, an anode disposed in the housing, a stabilized cathode disposed in the housing and comprising a cathode material. The cathode material comprises a composition selected from birnessite or layered-polymorph of manganese dioxide (δ-MnO 2 ), the composition being stabilized by bismuth and copper ions, a conductive carbon, and a binder. The anode can be at least 50% (m/m) lithium, magnesium, aluminum, or zinc.

Claims

exact text as granted — not AI-modified

What is claimed is:

1. A battery comprising:
a housing;
an electrolyte disposed in the housing;
an anode disposed in the housing, wherein the anode is at least 50% (m/m) lithium, magnesium, or aluminum;
a stabilized cathode disposed in the housing and comprising a cathode material, the cathode material comprising:
a composition selected from birnessite or layered-polymorph of manganese dioxide (δ-MnO 2 ), the composition being stabilized by bismuth and copper ions;
a conductive carbon; and
a binder.

2. The battery as recited in claim 1 , wherein the birnessite is synthesized through electrochemical, chemical, or heat treatment methods.

3. The battery as recited in claim 1 , wherein the stabilized cathode further comprises a metallic ion selected from the group consisting of tin, aluminum, nickel, iron, cobalt and lead.

4. The battery as recited in claim 1 , wherein the binder comprises a polytetrafluoroethylene, polyvinylidene fluoride, a cellulose-based hydrogel or a combination thereof.

5. The battery as recited in claim 1 , wherein the binder is a cellulose-based hydrogel selected from the group consisting of methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxypropylmethyl cellulose (HPMC), hydroxyethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (HEC).

6. The battery as recited in claim 5 , wherein the binder is a cellulose-based hydrogel crosslinked with a copolymer selected from the group consisting of polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole.

7. The battery as recited in claim 1 , wherein the conductive carbon is selected from the group consisting of TIMREX® Primary Synthetic Graphite, TIMREX® Natural Flake Graphite, TIMREX® MB, TIMREX® MK, TIMREX® MX, TIMREX® KC, TIMREX® B, TIMREX® LB, TIMREX® Dispersions; ENASCO 150G, ENASCO 210G, ENASCO 250G, ENASCO 260G, ENASCO 350G, ENASCO 150P, ENASCO 250P; SUPER P, SUPER P Li, carbon black, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, Zenyatta graphite and combinations thereof.

8. The battery as recited in claim 7 , wherein the conductive carbon further comprises a deposit of nickel, copper, tin, aluminum, cobalt, silver or nickel-phosphorous.

9. The battery as recited in claim 1 , where the cathode material is 1-98 wt. % stabilized birnessite, 1-98 wt. % conductive carbon and 1-10 wt. % binder.

10. The battery as recited in claim 1 , wherein the cathode material has a porosity between 5-95%.

11. The battery as recited in claim 1 , further comprising a current collector for the cathode material, the current collector selected from the group consisting of copper, aluminum, and nickel.

12. The battery as recited in claim 1 , wherein the electrolyte is an acidic electrolyte, an alkaline electrolyte, an ionic liquid, an organic-based electrolyte, a solid-phase electrolyte, a gelled electrolyte, or combinations thereof.

13. The battery as recited in claim 1 , wherein the electrolyte is selected from the group consisting of chlorides, sulfates, sodium hydroxide, potassium hydroxide, lithium hydroxide, a perchlorate, lithium perchlorate, magnesium perchlorate, aluminum perchlorate, lithium hexafluorophosphate, [M + ][AlCl 4 − ](M + )]-sulphonyl chloride, a phosphoryl chloride cation, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide, 1-hexyl-3-methylimidazolium hexofluorophosphate, 1-ethyl-3-methylimidazolium dicyanamide, 11-methyl-3-octylimidazolium tetrafluoroborate, yttria-stabilized zirconia, beta-alumina solid, polyacrylamides, NASICON, lithium salts in mixed organic solvents, 1,2-dimethoxyethane, propylene carbonate, magnesium bis(hexamethyldisilazide) in tetrahydrofuran and combinations thereof.

14. The battery as recited in claim 1 , further comprising a polymeric or ceramic separator between the anode and the cathode material.

15. A method of operating a battery comprising:
discharging a battery, wherein the battery comprises:
a housing;
an electrolyte disposed in the housing;
an anode disposed in the housing, wherein the anode is at least 50% (m/m) lithium, magnesium, or aluminum;
a stabilized cathode disposed in the housing and comprising a cathode material, the cathode material comprising:
a composition selected from birnessite or layered-polymorph of manganese dioxide (δ-MnO 2 ), the composition being stabilized by bismuth and copper ions;
a conductive carbon; and
a binder;

charging the battery; and
stabilizing the cathode with the bismuth and copper ions during the discharging and charging.

16. The method as recited in claim 15 , wherein the birnessite is synthesized through electrochemical, chemical, or heat treatment methods.

17. The method as recited in claim 15 , wherein the bismuth and copper ions are included directly after making birnessite.

18. The method as recited in claim 15 , wherein the stabilized cathode further comprises a metallic ion selected from the group consisting of tin, aluminum, nickel, iron, cobalt and lead.

19. The method as recited in claim 15 , wherein the binder comprises a polytetrafluoroethylene, polyvinylidene fluoride, a cellulose-based hydrogel or a combination thereof.

20. The method as recited in claim 15 , wherein the binder is a cellulose-based hydrogel selected from the group consisting of methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxypropylmethyl cellulose (HPMC), hydroxyethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (HEC).

21. The method as recited in claim 20 , wherein the binder is a cellulose-based hydrogel crosslinked with a copolymer selected from the group consisting of polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole.

22. The method as recited in claim 15 , wherein the conductive carbon is selected from the group consisting of TIMREX® Primary Synthetic Graphite, TIMREX® Natural Flake Graphite, TIMREX® MB, TIMREX® MK, TIMREX® MX, TIMREX® KC, TIMREX® B, TIMREX® LB, TIMREX® Dispersions; ENASCO 150G, ENASCO 210G, ENASCO 250G, ENASCO 260G, ENASCO 350G, ENASCO 150P, ENASCO 250P; SUPER P, SUPER P Li, carbon black, acetylene black, single walled carbon nanotubes, multi-walled carbon nanotubes, graphene, graphyne, graphene oxide, Zenyatta graphite and combinations thereof.

23. The method as recited in claim 22 , where in the conductive carbon further comprises a deposit of nickel, copper, tin, aluminum, cobalt, silver or nickel-phosphorous.

24. The method as recited in claim 15 , where the cathode material is 1-98 wt. % stabilized birnessite, 1-98 wt. % conductive carbon and 1-10 wt. % binder.

25. The method as recited in claim 15 , wherein the cathode material has a porosity between 5-95%.

26. The method as recited in claim 15 , further comprising a current collector for the cathode material, the current collector selected from the group consisting of copper, aluminum and nickel.

27. The method as recited in claim 15 , wherein the electrolyte is an acidic electrolyte, an alkaline electrolyte, an ionic liquid, an organic-based electrolyte, a solid-phase electrolyte, a gelled electrolyte, or combinations thereof.

28. The method as recited in claim 15 , wherein the electrolyte is selected from the group consisting of chlorides, sulfates, sodium hydroxide, potassium hydroxide, lithium hydroxide, a perchlorate, lithium perchlorate, magnesium perchlorate, aluminum perchlorate, lithium hexafluorophosphate, [M + ][AlCl 4 − ](M + )]-sulphonyl chloride, a phosphoryl chloride cation, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide, 1-hexyl-3-methylimidazolium hexofluorophosphate, 1-ethyl-3-methylimidazolium dicyanamide, 11-methyl-3-octylimidazolium tetrafluoroborate, yttria-stabilized zirconia, beta-alumina solid, polyacrylamides, NASICON, lithium salts in mixed organic solvents, 1,2-dimethoxyethane, propylene carbonate, magnesium bis(hexamethyldisilazide) in tetrahydrofuran and combinations thereof.

29. The method as recited in claim 15 , further comprising a polymeric or ceramic separator between the anode and the cathode material.

30. The method as recited in claim 15 , further comprising:
discharging and charging the battery at least 100 times, and
retaining a capacity of at least 150 mAh/g while discharging the batter after the discharging and charging at least the 100 times.

31. A battery comprising:
a housing;
an electrolyte disposed in the housing;
an anode disposed in the housing, wherein the anode is at least 50% (m/m) lithium;
a stabilized cathode disposed in the housing and comprising a cathode material, the cathode material comprising:
birnessite comprising bismuth ions and copper ions, wherein the birnessite is stabilized by bismuth and copper ions;
a conductive carbon; and
a binder.

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